Yusuke Sugiyama

Synthesis and Reactions of a Stable 1,2-Diaryl-1,2-dibromodisilene: A Precursor for Substituted Disilenes and a 1,2-Diaryldisilyne

Synthesis and isolation of the stable diaryldibromodisilene, Bbt(Br)SiSi(Br)Bbt, has been accomplished for the first time. The dibromodisilene underwent substitution reactions with organometallic reagents on the low-coordinated silicon atom to afford the corresponding substituted disilenes. Furthermore, the reaction of 1 with t-BuLi afforded the corresponding 1,2-diaryldisilyne, BbtSi[triple bond]SiBbt, the characters of which were revealed by spectroscopic and crystallographic analyses.

Silicon Nanosheets and Their Self-Assembled Regular Stacking Structure

Silicon nanomaterials are encouraging candidates for application to photonic, electronic, or biosensing devices, due to their size-quantization effects. Two-dimensional silicon nanosheets could help to realize a widespread quantum field, because of their nanoscale thickness and microscale area. However, there has been no example of a successful synthesis of two-dimensional silicon nanomaterials with large lateral size and oxygen-free surfaces. Here we report that oxygen-free silicon nanosheets covered with organic groups can be obtained by exfoliation of layered polysilane as a result of reaction with n-decylamine and dissolution in an organic solvent. The amine residues are covalently bound to the Si(111) planes. It is estimated that there is ca. 0.7 mol of residue per mole of Si atoms in the reaction product. The amine-modified layered polysilane can dissolve in chloroform and exfoliate into nanosheets that are 1-2 microm wide in the lateral direction and with thicknesses on the order of nanometers. The nanosheets have very flat and smooth surfaces due to dense coverage of n-decylamine, and they are easily self-assembled in a concentrated state to form a regularly stacked structure. The nanosheets could be useful as building blocks to create various composite materials.

Synthesis and Optical Properties of Monolayer Organosilicon Nanosheets

The synthesis of silicon nanosheets for fabricating electronic devices, without using conventional vacuum processes and vapor deposition, is challenging and is anticipated to receive significant attention for a wide range of applications. Here, we report the synthesis of oxygen-free, phenyl-modified organosilicon nanosheets with atomic thickness. In organic solvents, a consequence of this new silicon structure is its uniform dispersion and the possibility of exfoliation into unilamellar nanosheets. Light-induced photocurrent in [Si(6)H(4)Ph(2)] was observed, leading to the possibility of various organosilicon nonamaterials with useful properties.

Synthesis and modification of silicon nanosheets and other silicon nanomaterials.

Silicon nanomaterials and nanostructures exhibit different properties from those of bulk silicon materials based on quantum confinement effects. They are expected to lead to the development of new applications of silicon, in addition to wide use in semiconductor devices. Aside from industrial interest, intriguing issues of academic interest still remain with respect to the origins of their characteristic properties. Zero- and one-dimensional crystalline silicon nanomaterials have been synthesized, to date, by using many methods and there has been rapid progress in size control and modification procedures. However, there have been only a few examples of silicon nanomaterials with atomic-order thickness akin to carbon nanomaterials, such as two-dimensional silicon nanosheets. Moreover, mass production of silicon nanomaterials with relatively low cost is not easily achievable, due to the typically severe conditions required for fabrication, such as high temperature and ultralow pressure. Recently, we have developed a soft synthetic method for silicon nanosheets with chemical surface modification in a solution process. This review provides methods for the synthesis and modification of silicon nanosheets and other silicon nanomaterials with examples of their potential applications.

Preparation of Alkyl-Modified Silicon Nanosheets by Hydrosilylation of Layered Polysilane (Si6H6)

Alkyl-modified crystalline silicon nanosheets 2 were synthesized and maintained the crystal structure of a Si(111) plane, in which the dangling silicon bond is stabilized by capping with the alkyl group. 2 was characterized using UV-vis, Fourier transform-infrared, and X-ray photoelectron spectroscopies; X-ray diffraction; and X-ray absorption near edge structure analysis. A model structure is proposed that has a periodicity through the nanosheet surface.

Synthesis of kinetically stabilized 1,2-dihydrodisilenes.

Kinetically stabilized 1,2-dihydrodisilenes were successfully synthesized and isolated by the introduction of sterically protecting bulky aryl groups. These 1,2-dihydrodisilenes exhibit distinct Si═Si double-bond character in both solution and the solid state. The Si-H bonds in these 1,2-dihydrodisilenes exhibit higher s character than those of typical σ(4),λ(4)-hydrosilanes. Moderate heating of these 1,2-dihydrodisilenes in solution resulted in their isomerization to the corresponding trihydrodisilanes, with an intramolecular hydrogen migration as the rate-determining step.

Electron transport properties of Si nanosheets: Transition from direct tunneling to Fowler-Nordheim tunneling

We have characterized the electron transport properties of n-decylamine-functionalized Si nanosheets (NSs) using atomic force microscopy with a conductive cantilever under vacuum conditions at room temperature. Electrons are transported from the cantilever to the substrate through Si NSs. The Si NSs exhibit nonresonant tunneling; the transport mechanisms are based on direct tunneling at low bias voltages and Fowler–Nordheim tunneling at high bias voltages.

Si–C composite anode of layered polysilane (Si6H6) and sucrose for lithium ion rechargeable batteries

Silicon–carbon (Si–C) composites were formed by mixing layered polysilane with sucrose, and then sintering. The Si–C composites had a unique form, which consisted of Si plates coated onto carbon particles. These composites were completely different from other Si–C composites made from silicon powder, which consist of carbon-coated silicon particles. Electrodes consisting of Si–C composites made from layered polysilane had a high capacity and a high capacity retention compared to layered polysilane electrodes, because the layered polysilane attached to carbon particles had a higher conductivity than a simple mixture of layered polysilane and carbon powder.

Properties and Mechanism of Layered Polysilane (Si6H6) Anode

Layered polysilane (Si6H6) is graphite-like structure which has higher capacity than crystalline silicon. The rate of increase of the thickness of a layered polysilane electrode after 10 charge-discharge cycles was smaller than that for a Si powder electrode, although layered polysilane electrode has higher capacity. The structural changes of electrochemically lithiated and delithiated layered polysilane at room temperature were studied using X-ray diffraction and Raman spectroscopy. Layered polysilane became amorphous by insertion of lithium to 0 V, whereas insertion of lithium into crystalline silicon produces Li15Si4. Layered polysilane maintained the amorphous state during lithium insertion and deinsertion, whereas silicon changed between Li15Si4 and amorphous LixSi, which explains the smaller volume change of a layered polysilane electrode compared with a Si powder electrode.